JPH03100007A - Preparation of fluorovinyl copolymer - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a method for producing a new and useful fluorine-containing vinyl copolymer. More specifically, the present invention provides a simple method for producing a fluorine-containing vinyl copolymer having both a hydroxyl group and a siloxycarbonyl group, a specific reactive functional group (reactive polar group), or a hydroxyl group and a carboxyl group. Regarding.

The fluorine-containing vinyl copolymer obtained by the production method of the present invention can be used as a base resin component for paints, for films, for sealants, etc.
It can be used to prepare various curable resin compositions.

[Prior art] A fluorine-containing vinyl copolymer having hydroxyl groups is blended with an amine resin, polyisocyanate, etc. as a curing agent.
When used as a so-called curable resin composition for paints, etc., a carboxyl group is also introduced into the hydroxyl group-containing fluorine-containing vinyl copolymer to promote the curing reaction, that is, to act as an internal catalyst. It is desirable to do so.

Generally, in order to introduce a carboxyl group into a vinyl polymer, it is sufficient to (co)polymerize a vinyl monomer having a carboxyl group, but in the case of this type of fluorine-containing vinyl copolymer, , a fluorine-containing vinyl monomer, a hydroxyl group-containing vinyl monomer, a carboxyl group-containing vinyl monomer, and, if necessary, other monomers copolymerizable with these, to form a hydroxyl group and a carboxyl group. When attempting to prepare a copolymer containing both, a gelation reaction inevitably occurs during polymerization, making it impossible to obtain the desired copolymer.

For this purpose, for example, as disclosed in JP-A-58-136605, in order to prepare a fluorine-containing vinyl copolymer having both a hydroxyl group and a carboxyl group, a fluorine-containing vinyl copolymer having only a hydroxyl group is prepared in advance. Although a method has been adopted in which a copolymer is obtained in advance and then a dibasic acid anhydride is added to the hydroxyl group-containing vinyl copolymer, when such a method is followed, the reaction time is inevitably short. It is disadvantageous in that it is long and the color (color tone) of the desired copolymer obtained is poor.

[Problem to be solved by the invention]

However, in view of the existence of various drawbacks in the prior art as described above, the present inventors have attempted to eliminate all of these drawbacks, simplify the layering process, and completely eliminate the occurrence of gelation reactions. In order to find a method for producing a fluorine-containing vinyl copolymer that has both free hydroxyl groups and carboxyl groups, we have undertaken extensive research.

Therefore, the problem to be solved by the present invention is to solve the following problems: - With only one stage of polymerization reaction, without causing gelation, it is possible to combine a hydroxyl group and a siloxycarbonyl group, which can be called a precursor group of a carboxyl group. To provide a method for producing a fluorine-containing vinyl copolymer, which further comprises reacting the thus obtained fluorine-containing vinyl copolymer having both a hydroxyl group and a siloxycarbonyl group with a compound containing active hydrogen. Another object of the present invention is to provide a method for producing a fluorine-containing vinyl copolymer having both a hydroxyl group and a carboxyl group.

[Means to solve the problem]

Therefore, the inventors of the present invention focused on the problems to be solved by the invention as described above, and as a result of repeated studies,
By using a siloxycarbonyl group, that is, a vinyl monomer having a carboxyl group blocked with a silyl group (a vinyl monomer containing a siloxycarbonyl group) as a component of the copolymerization monomer, a gelation reaction can be achieved. A fluorine-containing vinyl copolymer having both a hydroxyl group and a siloxycarbonyl group can be obtained without causing the formation of siloxycarbonyl groups, and a compound having active hydrogen is then reacted with the fluorine-containing vinyl copolymer containing a hydroxyl group and a siloxycarbonyl group. The present invention was completed by discovering that the desired fluorine-containing vinyl copolymer having both a hydroxyl group and a carboxyl group can be obtained by separating and removing the silyl group.

That is, the present invention provides a fluorine-containing vinyl monomer (a), a hydroxyl group-containing vinyl monomer fb), and a siloxycarbonyl group-containing vinyl monomer (c), particularly those having a siloxycarbonyl group represented by the general formula The present invention aims to provide a method for producing a fluorine-containing vinyl copolymer having both a hydroxyl group and a siloxycarbonyl group, which comprises subjecting a monomer mixture containing a vinyl monomer as an essential component to a radical copolymerization reaction. In addition, the above monomers (a), (bl and (c)) are subjected to a radical copolymerization reaction, and then the resulting fluorine-containing vinyl copolymer having both a hydroxyl group and a siloxycarbonyl group is treated with active hydrogen. It is also an object of the present invention to provide a method for producing a fluorine-containing vinyl copolymer having both a hydroxyl group and a carboxyl group, which comprises reacting a compound fd) containing a hydroxyl group and a carboxyl group.

Here, the above-mentioned fluorine-containing vinyl monomer (a>
Examples include vinyl fluoride, vinylidene fluoride, trifluoroethylene, tetrafluoroethylene, chlorotrifluoroethylene, promotrifluoroethylene, pentafluoropropylene, or (per)fluoroalkyl group having 1 to 18 carbon atoms. ) Fluoroalkyl trifluorovinyl ether is a typical example.

In addition, examples of the hydroxyl group-containing vinyl monomer (b) include 2-hydroxyethyl vinyl ether, 3-hydroxypropyl vinyl ether, 2-hydroxypropyl vinyl ether, 4-hydroxybutyl vinyl ether, 3-hydroxypropyl vinyl ether,
-Hydroxybutyl vinyl ether, 2-hydroxy-
Various hydroxyalkyl vinyl ethers such as 2-methylpropyl vinyl ether, 5-hydroxypentyl vinyl ether or 6-hydroxyethyl vinyl ether; 4-hydroxycyclohexyl vinyl ether, 4-hydroxymethylcyclohexyl vinyl ether or 1-hydroxymethyl-4-vinyloxymethylcyclohexane Typical examples include vinyl ethers having both a hydroxyl group and a cycloalkyl ring, such as; , furthermore, 2-hydroxyethyl (
meth)acrylate, 2-hydroxypropyl(meth)
Various (meth)acrylic acid esters such as acrylate or 4-hydroxybutyl (meth)acrylate can be mentioned as representative examples, but among these, from the viewpoint of copolymerizability, hydroxyalkyl vinyl ethers, It is particularly desirable to use vinyl ethers having both a hydroxyl group and a cycloalkyl ring.

Strictly speaking, the above-mentioned hydroxyalkyl allyl ethers are other than the hydroxyl group-containing vinyl monomer, but should be understood to be included in the present invention.

Furthermore, the above-mentioned siloxycarbonyl group-containing vinyl monomer (c1, in particular, typical vinyl monomers having a siloxycarbonyl group represented by the general formula include trimethylsiloxy (meth)
Acrylate, triethylsiloxy(meth)acrylate, dimethylhydrosiloxy(meth)acrylate, diethylhydrosiloxy(meth)acrylate, triphenylsiloxy(meth)acrylate, tart-butyl-dimethylsiloxy(meth)acrylate, dimethylcyclohexylsiloxy( various siloxy(meth)acrylates such as meth)acrylate or tris(2-methoxyethyl)siloxy(meth)acrylate; various unsaturations such as bis(trimethylsilyl)malate, bis(trimethylsilyl)fumarate or bis(trimethylsilyl)itaconate Bissilyl esters of dibasic acids: or vinyl-3-trimethylsiloxycarbonylprobionate 5, vinyl-4-trimethylsiloxycarbonylbutanoate, vinyl-5-trimethylsiloxycarbonylpentanoate or vinyl-6
-monovinyl monosilyl esters of various saturated dibasic acids such as -trimethylsiloxycarponylhexanoate.

Therefore, in carrying out the method of the present invention, the above monomers (a) to fe) alone may be copolymerized, or if necessary, these monomers (a) to fc may be copolymerized.
) may also be carried out by a copolymerization reaction using other monomers copolymerizable with each monomer.

Examples of such copolymerizable monomers include methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, and tert-butyl. Various alkoxy vinyl ethers such as vinyl ether, n-pentyl vinyl ether, n-hexyl vinyl ether, n-octyl vinyl ether or 2-ethylhexy vinyl ether; various cycloalkyl vinyl ethers such as cyclopentyl vinyl ether, cyclohexyl vinyl ether or methylcyclohexyl vinyl ether: Vinyl acetate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, vinyl pivalate, vinyl caproate, vinyl persate, vinyl laurate,
Vinyl stearate, vinyl benzoate, p-tart
- Various carboxylic acid vinyl esters such as vinyl 7'-thylbenzoate or vinyl cyclohexanecarboxylate; various (meth)acrylics such as methyl (meth)acrylate, ethyl (meth)acrylate or n-butyl (meth)acrylate. Acid esters; or various α-olefins such as ethylene, propylene, 1-butene or 1-hexene, as well as vinyl chloride and vinylidene chloride.

In order to prepare a fluorine-containing vinyl copolymer having both a hydroxyl group and a siloxycarbonyl group using the various monomers listed above, 15 to 15 of the fluorine-containing vinyl monomer (a)
70% by weight, 1 to 4 of hydroxyl group-containing vinyl monomer Tb)
0% by weight, siloxycarbonyl group-containing vinyl monomer (c
) and 83.95% by weight of other copolymerizable monomers, preferably from 20 to 60% by weight of the monomers (20 to 60% by weight of the monomers 3 to 30% by weight of (b), 0.1 to 30% by weight of monomer (c),
The copolymerization reaction may be carried out in a proportion of 5 to 76.9% by weight of the monomer and other copolymerizable monomers.

As the radical polymerization initiator used in this case, known and commonly used ones can be used, but among them, only representative ones include azobisisobutyronitrile, abbisisovaleronitrile, or Various azo compounds such as azobis(2,4-dimethylvaleronitrile); or tsr t-butylperoxypivalate, tert-butylperoxybenzoate,
tert-butyl peroxy-2-ethylhexanoate, benzoyl peroxide, lauroyl peroxide, acetyl peroxide, di-tert-butyl peroxide, dicumyl peroxide, tert-
These include various peroxides such as butyl hydroperoxide, cumene hydroperoxide, methyl ethyl ethone peroxide or diisopropyl peroxycarbonate.

The amount of the radical polymerization initiator used is as follows:
It should be determined as appropriate depending on the type of polymerization initiator, polymerization temperature, or molecular weight of the resulting copolymer, but generally 0.0 of the total amount of monomers to be copolymerized.
It may be about 1 to 15% by weight.

In order to prepare a fluorine-containing vinyl copolymer having both a hydroxyl group and a siloxycarbonyl group by such a radical copolymerization reaction, either a bulk polymerization method or a solution polymerization method may be used. From the viewpoint of being usable as a coating composition, solution polymerization is particularly desirable.

Typical organic solvents used in solution polymerization include benzene, toluene,
Aromatic hydrocarbons such as xylene or ethylbenzene; aliphatic hydrocarbons such as n-pentane, n-hexane or n-octane; cycloaliphatic hydrocarbons such as cyclopentane, cyclohexane, methylcyclohexane or ethylcyclohexane; dimethoxy Ethers such as ethane, tetrahydrofuran, dioxane, diisopropyl ether or di-n-butyl ether; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl amyl ketone, cyclohexanone or isophorone; methyl acetate, ethyl acetate, n-propyl acetate , n-butyl acetate, isobutyl acetate,
Esters such as ethylene glycol monoethyl ether acetate or ethylene glycol monobutyl ether acetate; or chlorinated hydrocarbons such as chloroform, methylene chloride, trichloroethane or tetrachloroethane, as well as dimethylformamide or dimethylacetamide.

Of course, these may be used alone or in combination of two or more.

The amount used may be about 5 to 1,000 parts by weight based on 100 parts by weight of the total amount of monomers to be polymerized.

In order to prepare a fluorine-containing vinyl copolymer containing hydroxyl groups and siloxycarbonyl groups from each raw material component as listed above,
Any conventionally known method may be used, and if the fluorine-containing vinyl monomer (al) is gaseous at room temperature,
As the reaction vessel, a so-called closed type vessel such as an autoclave may be used.

Specific polymerization methods include (1) a method in which monomers, a radical polymerization initiator, and a solvent are charged all at once into a reaction vessel and polymerization is carried out; (2) a method in which a reaction vessel containing a solvent is charged;
A method in which monomers and a radical polymerization initiator are added at the same time to perform polymerization, or (2) a method in which a solvent, monomers, and a part of a radical polymerization initiator are charged into a reaction vessel and polymerization is started. , a method in which the remaining monomers and a radical polymerization initiator are added to continue the polymerization, and the like.

The reaction temperature at this time is appropriately selected depending on the type of radical polymerization initiator, the molecular weight of the resulting copolymer, etc., and may be approximately 20 to 150°C.

In addition, the reaction time at this time is determined appropriately depending on the type of monomer used, the polymerization reaction temperature, the type of radical polymerization initiator, etc., but it is generally about 3 to 30 hours. stomach.

First, a fluorine-containing vinyl copolymer having both a hydroxyl group and a siloxycarbonyl group is obtained.

Next, in order to prepare a fluorine-containing vinyl copolymer having both a hydroxyl group and a carboxyl group from such a fluorine-containing vinyl copolymer having both a hydroxyl group and a siloxycarbonyl group, simply add a compound having active hydrogen (dl). Just let it react.

Particularly representative examples of the active hydrogen-containing compound (d) used in this case include carboxylic acids such as formic acid, acetic acid, or propionic acid; metasulfonic acid, trifluorometasulfonic acid, and benzenesulfonic acid. acids or p-)sulfonic acids such as luenesulfonic acid; or inorganic acids such as hydrogen chloride, hydrogen fluoride, hydrogen bromide, sulfuric acid or phosphoric acid, as well as mono- or dialkyl esters of water or phosphoric acid. , or monoalkyl esters of phosphorous acid.

These can be used alone or in combination of two or more types.
Of course.

To prepare the final target product, a fluorine-containing vinyl copolymer having a hydroxyl group and a carboxyl group, from the active hydrogen-containing compound (d) and the fluorine-containing vinyl copolymer having a hydroxyl group and a siloxycarbonyl group as described above. What is necessary is to react a mixture of both at a temperature of about 0 to 150° C. while stirring.

The amount of the active hydrogen-containing compound fd) to be used in such a reaction is determined by determining what percentage of the siloxy groups contained in the fluorine-containing vinyl copolymer containing hydroxyl groups and siloxycarbonyl M is converted into carboxyl groups. It is determined as appropriate depending on the conversion rate.

For example, if it is desired to convert 100% into carboxyl groups, it is sufficient to react the active hydrogen-containing compound in an equivalent or more amount with the siloxy group.

When converting a siloxy group to a carboxyl group, a low molecular weight compound containing a silyl group, such as dimethylolsiloxane, is produced as a by-product. It may be allowed to remain in the target copolymer solution, or it may be removed through simple operations such as extraction or distillation.

Both the fluorine-containing vinyl copolymer having both a hydroxyl group and a siloxycarbonyl group and the fluorine-containing vinyl copolymer having both a hydroxyl group and a carboxyl group obtained in this way can be used with curing agents such as polyisocyanates and amino resins. It can be effectively used as a curable resin composition for paints, films, sealants, etc.

〔Effect of the invention〕

According to the method of the present invention, it is possible to easily produce a fluorine-containing vinyl copolymer having both a siloxycarbonyl group, that is, a carboxyl group blocked with a silyl group, and a hydroxyl group. A fluorine-containing copolymer having both a carboxyl group and a hydroxyl group can also be easily produced by reacting a polymer with a compound having active hydrogen, so the present invention is novel and extremely useful. It can be said that it is something.

The double fluorine-containing vinyl copolymer obtained in this way is
Since it can be used as a base resin component for paints, it can be said that the production method of the present invention has extremely high utility value.

〔Example〕

Next, the present invention will be explained in detail with reference to Examples and Comparative Examples.

In the following, unless otherwise specified, "%" is used as "%".
% by weight.

Examples 1 to 5 These examples are all preparation examples of fluorine-containing vinyl copolymers having both a hydroxyl group and a siloxycarbonyl group.

First, monomers other than the fluorine-containing vinyl monomer (a) as shown in Table 1, a radical polymerization initiator, and an organic solvent were placed in 11 stainless steel autoclaves that were sufficiently purged with nitrogen. I prepared it.

Furthermore, as an anti-gelling agent during the polymerization reaction, 1% of bis(1,2,26,6-
Bentamethyl-4-piperidinyl) sebacate was also charged.

Next, the liquefied and collected fluorine-containing vinyl monomer is injected,
While stirring, the temperature was maintained at 60°C for 15 hours to continue the polymerization reaction, and then the temperature was raised to 80°C and kept at the same temperature for 4 hours.
The mixture was held for a certain period of time and the reaction was further continued to obtain solutions of various desired copolymers.

However, when using tetrafluoroethylene as the fluorine-containing vinyl monomer (a), after pressurizing the amount of tetrafluoroethylene listed in the table in gaseous form,
The polymerization reaction was carried out as described above.

By analyzing the solution of each fluorine-containing vinyl copolymer thus obtained by gas chromatography,
The unreacted amount of the siloxycarbonyl group-containing vinyl monomer fb) was checked and calculated based on the data.
The polymerization rate of the siloxycarbonyl group-containing vinyl monomer is shown in the same table.

Similarly, the nonvolatile content and Gardner viscosity at 25° C. of each fluorine-containing vinyl copolymer solution are also shown together in the same table.

Comparative Examples 1 to 5 Instead of using trimethylsilyl acrylate, dimethylphenylsilyl methacrylate, or vinyl-5-trimethylsiloxycarbonylpentanoate as the siloxycarbonyl group-containing vinyl monomer (c),
modified to use acrylic acid, methacrylic acid, or adipic acid monovinyl ester, respectively, and
A control fluorine-containing vinyl copolymer was obtained in the same manner as in Examples 1 to 5, except that the amount of each monomer used was changed as shown in Table 2. It turned into a gel during polymerization.

/ / / / / / / / / Example 6 This example is an example of the preparation of a fluorine-containing vinyl copolymer having both a hydroxyl group and a carboxyl group.

First, 500 g of the copolymer solution obtained in Example 1 and 1 g of water were charged into a 1β reaction vessel, and the mixture was heated at 80° C. for 5 hours under stirring to react. A solution of the desired copolymer having a nonvolatile content of 52.0% and a viscosity of ST was obtained.

Next, apply this copolymer solution to a Br disk,
Under reduced pressure, volatiles were removed and the infrared absorption spectrum (
IR spectrum) analysis showed that it was 1.260 c.
The absorption based on 5i-Ct(,) disappears, and instead, a broad absorption based on carboxyl group appears at 3,200 to 2.600 cm'', indicating that the siloxycarbonyl group is a carboxyl group. It was confirmed that the .

Example 7 This example is also an example of the preparation of a fluorine-containing vinyl copolymer having both a hydroxyl group and a carboxyl group.

First, 50% of the copolymer solution obtained in Example 2 was prepared.
0g and 15g of formic acid into 11 reaction vessels,
When reacted by heating at 80°C for 5 hours in a nitrogen stream with stirring, the non-volatile content was 51.8%.
A solution of the desired copolymer having a viscosity of Z was obtained.

Example 6 shows that even in this copolymer solution, the siloxycarbonyl group is converted to a carboxyl group.
This was confirmed by the same IR spectrum analysis.

Example 8 This example is also an example of the preparation of a fluorine-containing copolymer having both hydroxyl and carboxyl groups. A nonvolatile content of 52.8% was prepared in the same manner as in Example 6, except that 500 g of the prepared copolymer solution was used, and 5 g of acetic acid was used as the active hydrogen-containing compound. A solution of the desired copolymer having a viscosity of ST was obtained.

As a result of IR spectrum analysis, in the copolymer of this example, the siloxycarbonyl groups were also converted to carboxyl groups, as in Examples 6 and 7.

Claims (1)

[Scope of Claims] 1. A monomer mixture containing a fluorine-containing vinyl monomer (a), a hydroxyl group-containing vinyl monomer (b), and a siloxycarbonyl group-containing vinyl monomer (c) as essential components. A method for producing a fluorine-containing vinyl copolymer having both a hydroxyl group and a siloxycarbonyl group, the method comprising subjecting the fluorine-containing vinyl copolymer to a radical copolymerization reaction. 2. A fluorine-containing vinyl monomer (a), a hydroxyl group-containing vinyl monomer (b), and a siloxycarbonyl group-containing vinyl monomer (c) are subjected to a radical copolymerization reaction, and then the hydroxyl group and siloxycarbonyl group obtained in this way are subjected to a radical copolymerization reaction. A method for producing a fluorine-containing vinyl copolymer having both a hydroxyl group and a carboxyl group, the method comprising reacting a fluorine-containing vinyl copolymer having both a hydroxyl group and a carboxyl group with a compound (d) containing an active hydrogen group. 3. The fluorine-containing vinyl monomer (a) described above is vinyl fluoride, vinylidene fluoride, trifluoroethylene, tetrafluoroethylene, chlorotrifluoroethylene, pentafluoropropylene, and has 1 to 4 carbon atoms (
Claims 1 and 2 are at least one compound selected from the group consisting of (per)fluoroalkyl trifluorovinyl ethers having a per)fluoroalkyl group.
The manufacturing method described in. 4. Claim 1, wherein the hydroxyl group-containing vinyl monomer (b) is at least one compound selected from the group consisting of hydroxyalkyl vinyl ethers and vinyl ethers having both a cycloalkyl ring and a hydroxyl group.
and the manufacturing method described in 2. 5. The above-mentioned siloxycarbonyl group-containing vinyl monomer (
c) is a general formula ▲ There are numerical formulas, chemical formulas, tables, etc. ▼ However, R_1, R_2 and R_4 in the formula are each independently a hydrogen atom, an alkyl group, a substituted alkyl group, a cycloalkyl group, a substituted cycloalkyl group. represents a group or an aromatic residue. It has a siloxycarbonyl group represented by
The manufacturing method according to claim 1 or 2.